EP4144890A1 - Procédé de production d'alcoolats alcalins dans une cellule d'électrolyse - Google Patents

Procédé de production d'alcoolats alcalins dans une cellule d'électrolyse Download PDF

Info

Publication number
EP4144890A1
EP4144890A1 EP21195069.6A EP21195069A EP4144890A1 EP 4144890 A1 EP4144890 A1 EP 4144890A1 EP 21195069 A EP21195069 A EP 21195069A EP 4144890 A1 EP4144890 A1 EP 4144890A1
Authority
EP
European Patent Office
Prior art keywords
sub
chamber
electrolytic cell
solution
solid electrolyte
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP21195069.6A
Other languages
German (de)
English (en)
Inventor
Philip Heinrich REINSBERG
Michael Horn
Rüdiger TEUFERT
Marc Weiner
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Evonik Operations GmbH
Original Assignee
Evonik Functional Solutions GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Evonik Functional Solutions GmbH filed Critical Evonik Functional Solutions GmbH
Priority to EP21195069.6A priority Critical patent/EP4144890A1/fr
Priority to EP22765897.8A priority patent/EP4399349A1/fr
Priority to PCT/EP2022/073158 priority patent/WO2023030920A1/fr
Priority to US18/688,762 priority patent/US12503783B2/en
Publication of EP4144890A1 publication Critical patent/EP4144890A1/fr
Withdrawn legal-status Critical Current

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B13/00—Diaphragms; Spacing elements
    • C25B13/04—Diaphragms; Spacing elements characterised by the material
    • C25B13/05—Diaphragms; Spacing elements characterised by the material based on inorganic materials
    • C25B13/07—Diaphragms; Spacing elements characterised by the material based on inorganic materials based on ceramics
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B3/00—Electrolytic production of organic compounds
    • C25B3/01—Products
    • C25B3/07—Oxygen containing compounds
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B3/00—Electrolytic production of organic compounds
    • C25B3/01—Products
    • C25B3/13—Organo-metallic compounds
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B3/00—Electrolytic production of organic compounds
    • C25B3/20—Processes
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B3/00—Electrolytic production of organic compounds
    • C25B3/20—Processes
    • C25B3/25—Reduction
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
    • C25B9/13—Single electrolytic cells with circulation of an electrolyte
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
    • C25B9/17—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof
    • C25B9/19—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof with diaphragms
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
    • C25B9/17—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof
    • C25B9/19—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof with diaphragms
    • C25B9/21—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof with diaphragms two or more diaphragms
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
    • C25B9/60—Constructional parts of cells

Definitions

  • the present invention relates to a method for producing an alkali metal alkoxide solution L 1 in an electrolytic cell E which comprises at least one cathode chamber K K , at least one anode chamber K A and optionally a central chamber K M located in between.
  • F has the surface O F , and a part O A/MK of this surface O F contacts the interior space I KM or the interior space I KA directly, and a part O KK of this surface O F contacts the interior space I KK directly.
  • the surface O A/MK and/or the surface O KK comprises at least part of a surface O F ⁇ .
  • O F ⁇ results from a pre-treatment step in which F is produced from an AFK F' with the surface O F' .
  • the surface O F ′ is removed by compressed air blasting with a solid blasting agent N AFK from F′ , and the AFK F with the surface O F comprising the surface O F ⁇ formed by the compressed air blasting is obtained.
  • Electrolysis to produce the alkali metal alkoxides with F instead of F' results in improved conductivity, which means that a lower voltage can be used at a constant current density.
  • the electrochemical production of alkali metal alkoxide solutions is an important industrial process that is used, for example, in DE 103 60 758 A1 , the U.S. 2006/0226022 A1 and the WO 2005/059205 A1 is described.
  • the principle of this process is reflected in an electrolytic cell in whose anode chamber there is a solution of an alkali salt, for example common salt or NaOH, and in whose cathode chamber there is the alcohol in question or a low-concentration alcoholic solution of the alkali metal alcoholate in question, for example sodium methoxide or sodium ethoxide.
  • the cathode compartment and the anode compartment are separated by a ceramic which conducts the alkali metal ion used, for example NaSICON or an analog for potassium or lithium.
  • a ceramic which conducts the alkali metal ion used, for example NaSICON or an analog for potassium or lithium.
  • chlorine is formed at the anode - if a chloride salt of the alkali metal is used - and hydrogen and alcohol ions are formed at the cathode.
  • the charge equalization takes place in that alkali metal ions from the central chamber into the cathode chamber via the ceramic that is selective for them hike.
  • the charge equalization between the middle chamber and the anode chamber takes place through the migration of cations when using cation exchange membranes or the migration of anions when using anion exchange membranes or through the migration of both types of ions when using non-specific diffusion barriers. This increases the concentration of the alkali metal alcoholate in the cathode chamber and the concentration of the sodium ions in the anolyte
  • WO 2014/008410 A1 describes an electrolytic process for the production of elemental titanium or rare earths. This process is based on the fact that titanium chloride is formed from TiO 2 and the corresponding acid, this reacts with sodium alcoholate to form titanium alcoholate and NaCl and is finally converted electrolytically to form elemental titanium and sodium alcoholate.
  • WO 2007/082092 A2 and WO 2009/059315 A1 describe processes for the production of biodiesel in which triglycerides are first converted into the corresponding alkali metal triglycerides with the aid of alcoholates electrolytically produced via NaSICON and in a second step are converted into glycerol and the respective alkali metal hydroxide with electrolytically produced protons.
  • a disadvantage of the electrolytic cells described in the prior art is that the resistance of the solid electrolyte ceramics used therein is relatively high. As a result, the specific energy consumption of the electrolytically produced materials increases and the energy-specific data (current, voltage) of the cell also deteriorate. Eventually the whole process becomes economically unviable.
  • the object of the present invention was therefore to provide a process for preparing an alkali metal alkoxide solution in an electrolytic cell which does not have this disadvantage.
  • a further disadvantage of conventional electrolytic cells in this technical field results from the fact that the solid electrolyte is not stable over the long term with respect to aqueous acids. This is problematic insofar as the pH drops in the anode chamber during electrolysis as a result of oxidation processes (for example when halogens are produced by disproportionation or by oxygen formation). These acidic conditions attack the NaSICON solid electrolyte, so the process cannot be used on an industrial scale.
  • Various approaches have been described in the prior art to address this problem.
  • WO 2012/048032 A2 and US 2010/0044242 A1 describe, for example, electrochemical processes for the production of sodium hypochlorite and similar chlorine compounds in such a three-chamber cell.
  • the cathode chamber and the middle chamber of the cell are separated by a cation-permeable solid electrolyte such as NaSICON.
  • the middle chamber is supplied with solution from the cathode chamber, for example.
  • the US 2010/0044242 A1 also describes in Figure 6 that solution from the middle compartment can be mixed with solution from the anode compartment outside the compartment to obtain sodium hypochlorite.
  • the DE 42 33 191 A1 describes the electrolytic production of alcoholates from salts and alcoholates in multi-chamber cells and stacks of several cells.
  • the WO 2008/076327 A1 describes a process for preparing alkali metal alkoxides.
  • a three-chamber cell is used, the middle chamber of which is filled with alkali metal alkoxide (see, for example, paragraphs [0008] and [0067] of WO 2008/076327 A1 ).
  • WO 2009/073062 A1 A similar arrangement is described in WO 2009/073062 A1 .
  • this arrangement has the disadvantage that the alkali metal alkoxide solution, which is consumed as a buffer solution and is continuously contaminated, is the desired product.
  • the central chamber is separated from the anode chamber by a diffusion barrier and from the cathode chamber by an ion-conducting ceramic. It occurs during electrolysis thus unavoidable for the formation of pH gradients and dead volumes. This can damage the ion-conducting ceramic and consequently increase the voltage requirement of the electrolysis and/or lead to breakage of the ceramic.
  • a further object of the present invention was therefore to provide an improved process for the electrolytic production of alkali metal alkoxide. This should not have the aforementioned disadvantages and should in particular ensure improved protection of the solid electrolyte against the formation of the pH gradient and more economical use of the educts compared to the prior art.
  • Figure 1A shows an alkali cation-conducting solid electrolyte ceramic F' ⁇ 19>, as provided according to step (i).
  • This has a surface O F' ⁇ 190>.
  • the surface O F' ⁇ 190> includes two sub-areas, in Figure 1A these are the opposite surfaces denoted by the references ⁇ 191> and ⁇ 192>, of which the rear ⁇ 192> is covered.
  • the AFK F' ⁇ 19> will, as in Figure 1B shown, arranged in a process chamber ⁇ 90> opposite a sandblaster ⁇ 40> in such a way that the partial surface area ⁇ 191> faces it, while the partial surface area ⁇ 192> faces away from it.
  • Figure 1C shows the step of sandblasting.
  • a jet of a solid blasting medium N ⁇ 30> is generated with the sandblaster ⁇ 40> and accelerated in the direction of the AFK F' ⁇ 19>.
  • AFK is removed as particle ⁇ 185> from F' ⁇ 19>.
  • This method step gives an AFK F ⁇ 18> whose surface O F ⁇ 180> comprises a partial surface O A/MK ⁇ 181> facing the sandblaster ⁇ 40> and a partial surface O KK ⁇ 182> facing away from the sandblaster ⁇ 40>.
  • O A/MK ⁇ 181> in turn comprises a partial area O F ⁇ ⁇ 183>, which was formed by sandblasting AFK from F' ⁇ 19>.
  • Figure 1D shows the AFK F ⁇ 18> obtained in this way, which is obtained after step (ii).
  • This has a surface O F ⁇ 180>.
  • the surface O F ⁇ 180> includes the two partial areas O A/MK ⁇ 181> and O KK ⁇ 182>.
  • F ⁇ 18> corresponds to F' ⁇ 19> or the surface O F ⁇ 180> corresponds to the surface O F' ⁇ 190> with the difference that O A/MK ⁇ 181> includes the partial area O F ⁇ ⁇ 183>.
  • S MF that is the mass-related specific surface area S M of the AFK F ⁇ 18>
  • S MF' that is the mass-related specific surface area S M of the AFK F' ⁇ 19>.
  • the Figure 2A shows an embodiment not according to the invention based on an electrolytic cell E , which is a two-chamber cell.
  • the electrolytic cell E comprises a cathode chamber K K ⁇ 12> and an anode chamber K A ⁇ 11>.
  • the anode chamber K A ⁇ 11> comprises an anodic electrode E A ⁇ 113> in the interior I KA ⁇ 112>, an inlet Z KK ⁇ 110> and an outlet A KA ⁇ 111>.
  • the cathode chamber K K ⁇ 12> comprises a cathodic electrode E K ⁇ 123> in the interior I KK ⁇ 122>, an inlet Z KK ⁇ 120> and an outlet A KK ⁇ 121>.
  • the electrolytic cell E is delimited by an outer wall W A ⁇ 80>.
  • the interior I KK ⁇ 122> is also separated from the interior I KA ⁇ 112> separated.
  • the NaSICON solid electrolyte ceramic F' ⁇ 19> extends over the entire depth and height of the two-chamber cell E.
  • the NaSICON solid electrolyte ceramic F' ⁇ 19> contacts the two interior spaces I KK ⁇ 122> and I KA ⁇ 112> directly via the partial surfaces ⁇ 192> or ⁇ 191>, so that sodium ions can be conducted from one interior space to the other through the NaSICON solid electrolyte ceramic F' ⁇ 19>.
  • the respective sodium ions can be conducted from one interior space to the other through the NaSICON solid electrolyte ceramic F' ⁇ 19>.
  • Alkaline cation-conducting solid electrolyte ceramics F' ⁇ 19> or F ⁇ 18> are arranged in the respective electrolytic cell in such a way that the darkened area in Figures 1A and 1D faces the viewer in Figures 2A and 2B.
  • An aqueous solution of sodium chloride L 3 ⁇ 23> with pH 10.5 is added counter to gravity into the interior I KA ⁇ 112> via the inlet Z KA ⁇ 110>.
  • a solution of sodium methoxide in methanol L 2 ⁇ 22> is fed into the interior space I KK ⁇ 122> via the inlet Z KK ⁇ 120>.
  • a voltage is applied between the cathodic electrode E K ⁇ 123> and the anodic electrode E A ⁇ 113>.
  • methanol in the electrolyte L 2 ⁇ 22> is reduced to methoxide and H 2 (CH 3 OH + e - ⁇ CH 3 O - + 1 ⁇ 2 H 2 ).
  • Sodium ions diffuse from the interior I KA ⁇ 112> through the NaSICON solid electrolyte F ⁇ 18> into the interior I KK ⁇ 122>.
  • FIG 2B shows an embodiment of the method according to the invention.
  • the electrolytic cell E ⁇ 1> corresponds to that in Figure 2A shown arrangement with the difference that a NaSICON solid electrolyte ceramic F ⁇ 18> with the surface O F ⁇ 180> pretreated with the method according to Figures 1 A to 1 D is used as the partition wall W ⁇ 16>.
  • F ⁇ 18> has a partial surface O KK ⁇ 182> directly contacting the interior space I KK ⁇ 122> and a partial surface O A/MK ⁇ 181> directly contacting the interior space I KA ⁇ 112>.
  • the NaSICON solid electrolyte F ⁇ 18> is obtained from the NaSICON solid electrolyte F' ⁇ 19> by the sandblasting process shown in Figures 1 A to 1 D and, in contrast to F' ⁇ 19>, has the partial area O F ⁇ ⁇ 183>, formed on the partial surface O A/MK ⁇ 181> by the sandblasting process.
  • the NaSICON solid electrolyte ceramic F ⁇ 18> has a larger mass-related specific surface area S MF than that ( S MF' ) of the alkali cation-conducting solid electrolyte ceramic F' ⁇ 19>. This leads to better conductivity, i.e. a reduction in voltage with the same current during electrolysis, which leads to energy savings.
  • FIG. 3A shows a further embodiment of the method according to the invention.
  • the three-chamber electrolytic cell E ⁇ 1> comprises a cathode chamber K K ⁇ 12>, an anode chamber K A ⁇ 11> and a middle chamber K M ⁇ 13> located therebetween.
  • the anode chamber K A ⁇ 11> comprises an anodic electrode E A ⁇ 113> in the interior I KA ⁇ 112>, an inlet Z KK ⁇ 110> and an outlet A KA ⁇ 111>.
  • the cathode chamber K K ⁇ 12> comprises a cathodic electrode E K ⁇ 123> in the interior I KK ⁇ 122>, an inlet Z KK ⁇ 120> and an outlet A KK ⁇ 121>.
  • the middle chamber K M ⁇ 13> comprises an interior space I KM ⁇ 132>, an inlet Z KM ⁇ 130> and an outlet A KM ⁇ 131>.
  • the interior space I KA ⁇ 112> is connected to the interior space I KM ⁇ 132> via the connection V AM ⁇ 15>.
  • the electrolytic cell E ⁇ 1> is delimited by an outer wall W A ⁇ 80>.
  • the interior I KK ⁇ 122> is also separated from the interior I KM ⁇ 132> by a partition wall W ⁇ 16>, which consists of a disk of a NaSICON solid electrolyte ceramic F ⁇ 18> that is selectively permeable for sodium ions and has the surface O F ⁇ 180> separated.
  • This has a partial surface O KK ⁇ 182> directly contacting the interior space I KK ⁇ 122> and a partial surface O A/MK ⁇ 181> directly contacting the interior space I KM ⁇ 132>.
  • F ⁇ 18> extends over the entire depth and height of the three-chamber cell E ⁇ 1>.
  • F ⁇ 18> is obtained from the NaSICON solid electrolyte ceramic F' ⁇ 19> by a sandblasting process which corresponds to the process shown in Figures 1A to 1D and, in contrast to F' ⁇ 19>, has the partial area O F ⁇ ⁇ 183> , which is formed on the partial surface O A/MK ⁇ 181> by the sandblasting method.
  • the NaSICON solid electrolyte ceramic F ⁇ 18> shown is the surface O F ⁇ ⁇ 183> in the NaSICON solid electrolyte ceramic F ⁇ 18> obtained by method step (ii).
  • the NaSICON solid electrolyte ceramic F ⁇ 18> has an even greater mass-related specific surface area S MF than that ( S MF' ) of the alkali cation-conducting solid electrolyte ceramic F' ⁇ 19>. This leads to even better conductivity.
  • the NaSICON solid electrolyte ceramic F ⁇ 18> contacts the two inner spaces I KK ⁇ 122> and I KM ⁇ 132> directly, so that sodium ions can be conducted from one inner space to the other through the NaSICON solid electrolyte ceramic F ⁇ 18>.
  • the interior I KM ⁇ 132> of the middle chamber K M ⁇ 13> is additionally separated from the interior I KA ⁇ 112> of the anode chamber KA ⁇ 11> by a diffusion barrier D ⁇ 14>.
  • the NaSICON solid electrolyte F ⁇ 18> and the diffusion barrier D ⁇ 14> extend over the entire depth and height of the three-chamber cell E ⁇ 1>.
  • the diffusion barrier D ⁇ 14> is a cation exchange membrane (sulfonated PTFE).
  • connection V AM ⁇ 15> is formed outside the electrolytic cell E ⁇ 1>, in particular by a tube or hose, the material of which can be selected from rubber, metal or plastic.
  • liquid can be conducted from the interior I KM ⁇ 132> of the central chamber K M ⁇ 13> into the interior I KA ⁇ 112> of the anode chamber KA ⁇ 11> outside the three-chamber cell E ⁇ 1>.
  • connection V AM ⁇ 15> connects an outlet A KM ⁇ 131>, which breaks through the outer wall WA ⁇ 80> of the electrolytic cell E ⁇ 1> at the bottom of the central chamber K M ⁇ 13>, with an inlet Z KA ⁇ 110>, which breaks through the outer wall W A ⁇ 80> of the electrolytic cell E at the bottom of the anode chamber K A ⁇ 11>.
  • An aqueous solution of sodium chloride L 3 ⁇ 23> with pH 10.5 is added via the inlet Z KM ⁇ 130> in the same direction as gravity into the interior I KM ⁇ 132> of the central chamber K M ⁇ 13>.
  • the interior space I KM ⁇ 132 is formed by the connection V AM ⁇ 15>, which is formed between the outlet A KM ⁇ 131> of the central chamber K M ⁇ 13> and an inlet Z KA ⁇ 110> of the anode chamber KA ⁇ 11>> of the middle chamber K M ⁇ 13> connected to the interior I KA ⁇ 112> of the anode chamber K A ⁇ 11>.
  • Sodium chloride solution L 3 ⁇ 23> is conducted through this connection V AM ⁇ 15> from interior I KM ⁇ 132> to interior I KA ⁇ 112>.
  • a solution of sodium methoxide in methanol L 2 ⁇ 22> is fed into the interior space I KK ⁇ 122> via the inlet Z KK ⁇ 120>.
  • a voltage is applied between the cathodic electrode E K ⁇ 123> and the anodic electrode E A ⁇ 113>.
  • methanol in the electrolyte L 2 ⁇ 22> is reduced to methoxide and H 2 (CH 3 OH + e - ⁇ CH 3 O - + 1 ⁇ 2 H 2 ).
  • Sodium ions diffuse from the interior I KM ⁇ 132> of the middle chamber K M ⁇ 103> through the NaSICON solid electrolyte F ⁇ 18> into the interior I KK ⁇ 122>.
  • the acidity would damage the NaSICON solid electrolyte ceramic F ⁇ 18>, but is limited to the anode chamber K A ⁇ 11> by the arrangement in the three-chamber cell and is thus kept away from the NaSICON solid electrolyte ceramic F ⁇ 18> in the electrolytic cell E. This increases their lifespan considerably.
  • the Figure 3B shows a further embodiment of the method according to the invention. This is carried out in an electrolysis cell E ⁇ 1>, which is of the type shown in Figure 3 A shown electrolytic cell corresponds to E ⁇ 1> with the following difference:
  • the connection V AM ⁇ 15> from the interior I KM ⁇ 132> of the middle chamber K M ⁇ 13> to the interior I KA ⁇ 112> of the anode chamber K A ⁇ 11> is not outside, but through a perforation in the diffusion barrier D ⁇ 14> formed within the electrolytic cell E ⁇ 1>.
  • This perforation can be introduced into the diffusion barrier D ⁇ 14> subsequently (e.g. by stamping, drilling) or can already be present in the diffusion barrier D ⁇ 14> from the outset due to the production thereof (eg in the case of textile fabrics such as filter cloths or metal fabrics).
  • Figure 4 shows the increase in conductivity of a NaSICON ceramic that has been sandblasted according to step (ii). Shown is the respective current-voltage curve of an untreated NaSICON and two pretreated NaSICON ceramics in a three-chamber cell with 20% NaCl as anolyte and 10% sodium methylate as catholyte at about 60 °C.
  • the three ceramics are pieces of a large pottery, two of which have been sandblasted while one has been left untreated.
  • the x-axis shows the current (in mA), the y-axis shows the voltage (in volts).
  • “ ⁇ ” indicates the stress curve of an untreated NaSICON ceramic (comparison).
  • " ⁇ ” and “ ⁇ ” indicate the stress curve of the two sandblasted NaSICON ceramics.
  • “AFK” alkali cation-conducting solid electrolyte ceramic
  • step (i) The AFK F′ provided in step (i) is subjected to step (ii) in the method according to the invention, and after step (ii) the AFK F with the surface O F is obtained. Since F is essentially obtained from F' by removing a portion of AFK from F' in step (ii) to arrive at F , F' and F have essentially the same chemical structure.
  • any solid electrolyte through which cations, in particular alkali cations, more preferably sodium cations, can be transported from I AK to I KK or from I MK to I KK can be used as the alkali cation-conducting solid electrolyte ceramic F', and in particular also F.
  • Such solid electrolytes are known to those skilled in the art and, for example, in DE 10 2015 013 155 A1 , in the WO 2012/048032 A2 , paragraphs [0035], [0039], [0040], in the US 2010/0044242 A1 , paragraphs [0040], [0041], in which DE 10360758 A1 , paragraphs [014] to [025].
  • NaSICON LiSICON
  • KSICON KSICON
  • a sodium ion conductive solid electrolyte ceramic F' is preferred, with this even more preferably having a NaSICON structure.
  • NaSICON structures that can be used according to the invention are also used, for example, by Anantharamulu N, Koteswara Rao K, Rambabu G, Vijaya Kumar B, Velchuri Radha, Vithal M, J Mater Sci 2011, 46, 2821-2837 described.
  • the alkali cation-conducting solid electrolyte ceramic F' has a NaSICON structure of the formula M I 1+2w+x-y+z M II w M III x Zr IV 2-wxy M V y (SiO 4 ) z (PO 4 ) 3-z on.
  • M I is selected from Na + , Li + , preferably Na + .
  • M II is a divalent metal cation, preferably selected from Mg 2+ , Ca 2+ , Sr 2+ , Ba 2+ , Co 2+ , Ni 2+ , more preferably selected from Co 2+ , Ni 2+ .
  • M III is a trivalent metal cation, preferably selected from Al 3+ , Ga 3+ , Sc 3+ , La 3+ , Y 3+ , Gd 3+ , Sm 3+ , Lu 3+ , Fe 3+ , Cr 3+ , more preferably selected from Sc 3+ , La 3+ , Y 3+ , Gd 3+ , Sm 3+ , particularly preferably selected from Sc 3+ , Y 3+ , La 3+ .
  • M V is a pentavalent metal cation, preferably selected from V 5+ , Nb 5+ , Ta 5+ .
  • w, x, y, z are real numbers, where 0 ⁇ x ⁇ 2, 0 ⁇ y ⁇ 2, 0 ⁇ w ⁇ 2, 0 ⁇ z ⁇ 3, and where w, x, y, z are so chosen become that 1 + 2w + x - y + z ⁇ 0 and 2 - w - x - y ⁇ 0.
  • the solid electrolyte ceramics F′ and F which conduct alkali cations have the same structure.
  • step (ii) of the method according to the invention part of the alkali cation-conducting solid electrolyte ceramic F' is removed by jetting compressed air with a solid abrasive N.
  • an alkali cation-conducting solid electrolyte ceramic F with the surface O F is obtained, the surface O F differing from the surface O F ' in at least a partial area O F ⁇ and the surface O F comprising the surfaces O A / MK and O KK , where O A/MK and/or O KK comprise at least part of O F ⁇ .
  • step (ii) AFK is partially removed from F' by the sandblasting.
  • compressed air blasting with a solid blasting medium N includes inflation, in particular with compressed air.
  • AFK AFK is removed from F'
  • the extent to which AFK is removed from F' can be controlled by a person skilled in the art, for example via the selection of the solid blasting agent N, the pressure set and the time over which F' is sandblasted.
  • the pressure here is in particular >1 bar, preferably 2 to 10 bar, even more preferably 6 bar.
  • solid blasting agents customary in industry, in particular sand, blast furnace slag, glass granules, corundum, steel, plastic granules, nut shells, fruit stones, soda, ice crystals or CO 2 snow pellets can be used as the solid blasting agent N.
  • Glass granules are preferred, which are even more preferably spherical glass granules.
  • the duration over which the surface O F ' is sandblasted with the solid blasting agent N is in particular >1 min, preferably more than 30 min, preferably more than 60 min, even more preferably more than 120 min.
  • the AFK F′ when treating the surface of a specific body, in the context of the invention the AFK F′, this is arranged in a suitable process chamber and then the solid blasting medium is applied via a suitable nozzle.
  • the entire surface O F ' can be treated.
  • step (ii) If the entire surface O F ' is treated according to step (ii), the surface O F of the obtained AFK F differs completely from O F ' , ie O F and O F ⁇ are identical.
  • only part of the surface O F ' can also be treated in step (ii). This is possible, for example, by treating only part of the surface O F ′ , in particular by blasting it with the solid blasting medium N under compressed air, and AFK is removed only on this part of the surface O F ′ .
  • part of the surface O F' can also be covered with a stencil, so that only part of the surface O F' is removed from that in step (ii). In this case, an AFK F is obtained whose surface O F is still partially identical to the surface O F ' of F' and differs in part O F ⁇ from O F' .
  • O F ⁇ can form a contiguous subregion on the surface O F .
  • O F ⁇ can be formed by several unconnected partial areas on the surface O F so that their shape is pronounced of the shape of the black spots (corresponds to O F ⁇ ) on the white coat (corresponds to O F ) of the dog breed "Dalmatian".
  • step (ii) gives an AFK F which, compared to the AFK F' used in step (ii) when used in the electrolytic cell E according to step (iii) and step (iv- a) or (iv- ⁇ ) has a higher conductivity.
  • S MF ' is the mass-related specific surface area S M of the alkali cation-conducting solid electrolyte ceramic F' before step (ii) is carried out and where S MF is the mass-related specific surface area S M of the alkali cation-conducting solid electrolyte ceramic F after it has been carried out of step (ii).
  • S MF ' is the mass-related specific surface area S M of the alkali cation-conducting solid electrolyte ceramic F after it has been carried out of step (ii).
  • the comparison of the mass-related specific surfaces S MF' and S MF ie the examination of the condition whether S MF' ⁇ S MF , can be determined using methods known to those skilled in the art for measuring the BET (Brunauer-Emmett-Teller) surface area, as long as both AFK F and F' are measured under the same conditions. Even if the ratio of the two parameters S MF' and S MF is determined under different measurement conditions, the ratio S MF / S MF' measured under certain measurement conditions will essentially be the same as the ratio S MF / S MF' measured under other measurement conditions.
  • BET Brunauer-Emmett-Teller
  • the mass-related specific surface areas are carried out via BET measurements according to ISO 9277:2010 with N 2 (purity 99.99% by volume) as the adsorbent at 77.35 K.
  • Device Quantachrome NOVA 2200e, Quantachrome Instruments.
  • Sample preparation degassing of the sample at 60 °C at 1 Pa. The evaluation is carried out in particular using the static volumetric method (according to point 6.3.1 of the ISO 9277:2010 standard).
  • the ratio S MF ' and S MF ie the quotient S MF / S MF ' : S MF / S MF' ⁇ 1.01, preferably S MF / S MF' ⁇ 1.1, preferably S MF / S MF' ⁇ 1.5, preferably S MF / S MF' ⁇ 2.0, preferably S MF / S MF' ⁇ 3.0, preferably S MF / S MF' ⁇ 5.0, preferably S MF / S MF' ⁇ 10, more preferably S MF / S MF' ⁇ 20, more preferably S MF / S MF' ⁇ 50, more preferably S MF / S MF' ⁇ 100, more preferably S MF / S MF' ⁇ 150, more preferably S MF / S MF' ⁇ 200, more preferably S MF / S MF' ⁇ 500, more preferably S MF /
  • the quotient S MF / S MF' is in the range from 1.01 to 1000, preferably in the range from 1.1 to 50, more preferably in the range from 1.2 to 20, more preferably in the range from 1.3 to 15. more preferably in the range of 1.4 to 10, more preferably in the range of 1.5 to 5, more preferably in the range of 2.0 to 3.5, more preferably in the range of 2.8 to 3.2.
  • step (iii) of the process according to the invention the AFK F obtained in step (ii) is arranged in an electrolysis cell E.
  • the electrolytic cell E comprises at least one anode chamber K A and at least one cathode chamber K K and optionally at least one intermediate chamber K M .
  • This also includes electrolytic cells E which have more than one anode chamber K A and/or more than one cathode chamber K K and/or more than one middle chamber K M .
  • Such electrolytic cells, in which these chambers are joined together in a modular manner, are, for example, in DD 258 143 A3 and the U.S. 2006/0226022 A1 described.
  • the electrolytic cell E comprises an anode chamber K A and a cathode chamber K K and optionally a middle chamber K M located in between.
  • the electrolytic cell E usually has an outer wall W A .
  • the outer wall W A is in particular made of a material selected from the group consisting of steel, preferably rubberized steel, plastic, in particular Telene ® (thermosetting polydicyclopentadiene), PVC (polyvinyl chloride), PVC-C (post-chlorinated polyvinyl chloride), PVDF (polyvinylidene fluoride ) is selected.
  • W A can be perforated in particular for inlets and outlets.
  • Within W A then lie the at least one anode chamber K A , the at least one cathode chamber K K and, in the embodiments in which the electrolytic cell E comprises such, the at least one intermediate chamber K M .
  • the cathode chamber K K has at least one inlet Z KK , at least one outlet A KK and an interior space I KK , which includes a cathodic electrode E K .
  • the interior I KK of the cathode chamber K K is separated by the partition W from the interior I KA of the anode chamber K A if the electrolytic cell E does not include a central chamber K M .
  • the dividing wall W includes the alkali cation-conducting solid electrolyte ceramic F , and F then directly contacts the interior space I KK via the surface O KK and the interior space I KA via the surface O A/MK .
  • the interior I KK of the cathode chamber K K is separated by the partition W from the interior I KM of the middle chamber K M if the electrolytic cell E comprises at least one middle chamber K M .
  • the partition W includes the alkali cation-conducting solid electrolyte ceramic F , and F then directly contacts the interior space I KK via the surface O KK and the interior space I KM via the surface O A/MK .
  • the partition wall W comprises the solid electrolyte ceramic F which conducts alkali cations.
  • the feature "partition wall” means that the partition wall W is liquid-tight. This means in particular that the alkali cation-conducting solid electrolyte ceramic F enclosed by the partition wall completely separates the interior I KK and the interior I KM or the interior I KK and the interior I KA from one another, or comprises several alkali cation-conducting solid electrolyte ceramics which, for example, adjoin one another without gaps.
  • Direct contact means for the arrangement of the alkali cation-conducting solid electrolyte ceramics in the partition wall W and in the electrolytic cell E as well as for the surfaces O KK and O A/MK that there is an imaginary path from I KK to I AK or from I KK to I MK , which leads completely from I KK via O KK through F to O A/MK and finally in I AK or I MK .
  • At least 1% of the surface O A/MK is formed by O F ⁇ and/or, in particular and, at least 1% of the surface O KK is formed by O F ⁇ .
  • At least 10% of the surface area O A/MK is formed by O F ⁇ and/or, in particular and, at least 10% of the surface area O KK is formed by O F ⁇ .
  • At least 25% of the surface area O A/MK is formed by O F ⁇ and/or, in particular and, at least 25% of the surface area O KK is formed by O F ⁇ .
  • At least 40% of the surface area O A/MK is formed by O F ⁇ and/or, in particular and, at least 40% of the surface area O KK is formed by O F ⁇ .
  • At least 50% of the surface O A/MK is formed by O F ⁇ and/or, in particular and, at least 50% of the surface O KK is formed by O F ⁇ .
  • At least 60% of the surface O A/MK is formed by O F ⁇ and/or, in particular and, at least 60% of the surface O KK is formed by O F ⁇ .
  • At least 70% of the surface area O A/MK is formed by O F ⁇ and/or, in particular and, at least 70% of the surface area O KK is formed by O F ⁇ .
  • At least 80% of the surface area O A/MK is formed by O F ⁇ and/or, in particular and, at least 80% of the surface area O KK is formed by O F ⁇ .
  • At least 90% of the surface O A/MK is formed by O F ⁇ and/or, in particular and, at least 90% of the surface O KK is formed by O F ⁇ .
  • 100% of the surface O A/MK is formed by O F ⁇ and/or, in particular and, 100% of the surface O KK is formed by O F ⁇ .
  • the cathode chamber K K includes an interior space I KK , which in turn includes a cathodic electrode E K .
  • a cathodic electrode E K Any electrode familiar to a person skilled in the art that is stable under the conditions of the method according to the invention can be used as such a cathodic electrode E K .
  • This electrode E K can be selected from the group consisting of mesh wool, three-dimensional matrix structure or "balls”.
  • the cathodic electrode E K includes in particular a material selected from the group consisting of steel, nickel, copper, platinum, platinized metals, palladium, palladium supported on carbon, titanium. E K preferably comprises nickel.
  • the cathode chamber K K also includes an inlet Z KK and an outlet A KK .
  • the inlet Z KK and the outlet A KK are attached to the cathode chamber K K in such a way that the liquid makes contact with the cathodic electrode E K as it flows through the interior I KK of the cathode chamber K K .
  • the inlet Z KK and the outlet A KK can be attached to the electrolytic cell E by methods known to those skilled in the art, for example through bores in the outer wall W A and corresponding connections (valves) that simplify the introduction and removal of liquid.
  • the anode chamber K A has at least one inlet Z KA , at least one outlet A KA and an interior space I KA , which includes an anodic electrode E A .
  • the interior space I KA of the anode chamber K A is separated from the interior space I KM of the center chamber K M by a diffusion barrier D if the electrolytic cell E includes a central chamber K M .
  • the electrolytic cell E does not include a middle chamber K M , the interior space I KA of the anode chamber K is separated by the partition wall W from the interior space I KK of the cathode chamber K K .
  • the anode chamber K A includes an interior space I KA , which in turn includes an anodic electrode E A .
  • Any electrode familiar to a person skilled in the art that is stable under the conditions of the method according to the third aspect of the invention can be used as such an anodic electrode E A .
  • Such are in particular in WO 2014/008410 A1 , paragraph [024] or DE 10360758 A1 , paragraph [031].
  • This electrode E A can consist of one layer or of several planar, mutually parallel layers, each perforated or can be expanded.
  • the anodic electrode E A comprises in particular a material which is selected from the group consisting of ruthenium oxide, iridium oxide, nickel, cobalt, nickel tungstate, nickel titanate, noble metals such as platinum in particular, which is deposited on a carrier such as titanium or Kovar® (an iron/nickel/ Cobalt alloy, in which the individual proportions are preferably as follows: 54% by mass iron, 29% by mass nickel, 17% by mass cobalt) is supported.
  • Other possible anode materials are, in particular, stainless steel, lead, graphite, tungsten carbide, titanium diboride.
  • the anodic electrode E A preferably comprises a titanium anode (RuO 2 +IrO 2 /Ti) coated with ruthenium oxide/iridium oxide.
  • the anode chamber K A also includes an inlet Z KA and an outlet A KA .
  • the inlet Z KA and the outlet A KA are attached to the anode chamber K A in such a way that the liquid makes contact with the anodic electrode E A as it flows through the interior space I KA of the anode chamber K A .
  • This is the prerequisite for the solution L 4 being obtained at the outlet A KA when the method according to the invention is carried out if the solution L 3 of a salt S is passed through the interior space I KA of the anode chamber KA .
  • the inlet Z KA and the outlet A KA can be attached to the electrolytic cell E by methods known to those skilled in the art, eg through bores in the outer wall W A and corresponding connections (valves) that simplify the introduction and removal of liquid.
  • the inflow Z KA can also lie within the electrolytic cell, for example as a perforation in the diffusion barrier D .
  • the electrolytic cell E preferably has a central chamber K M .
  • the optional middle chamber K M is located between the cathode chamber K K and the anode chamber K A .
  • the interior space I KA of the anode chamber K A is separated from the interior space I KM of the center chamber K M by a diffusion barrier D if the electrolytic cell E includes a central chamber K M .
  • a KM is then also connected to the inlet Z KA by a connection V AM , so that liquid can be conducted from I KM into I KA through the connection V AM .
  • the interior I KM of the optional central chamber K M is separated from the interior I KA of the anode chamber K A by a diffusion barrier D and is separated from the interior I KK of the cathode chamber K K by the partition W.
  • any material which is stable under the conditions of the method according to the invention and which prevents or slows down the transfer of protons from the liquid located in the interior I KA of the anode chamber K A to the interior I KM of the optional central chamber K M can be used for the diffusion barrier D.
  • a non-ion-specific dividing wall or a membrane permeable to specific ions is used as the diffusion barrier D.
  • the diffusion barrier D is preferably a non-ion-specific partition.
  • the material of the non-ion-specific partition wall is in particular selected from the group consisting of fabric, in particular textile fabric or metal fabric, glass, in particular sintered glass or glass frits, ceramic, in particular ceramic frits, membrane diaphragms, and is selected particularly preferably a textile fabric or metal fabric, particularly preferably a textile fabric.
  • the textile fabric preferably comprises plastic, more preferably a plastic selected from PVC, PVC-C, polyvinyl ether (“PVE”), polytetrafluoroethylene (“PTFE”).
  • the diffusion barrier D is a “membrane that is permeable to specific ions”
  • the respective membrane favors the diffusion of certain ions through it compared to other ions.
  • specific ion permeable membranes also favor the diffusion of certain ions having one charge type through them over other ions of the same charge type.
  • the diffusion barrier D is a “membrane permeable to specific ions”, the diffusion barrier D is in particular an anion-conducting membrane or a cation-conducting membrane.
  • anion-conducting membranes are those which selectively conduct anions, preferably selectively specific anions. In other words, they favor the diffusion of anions through them over that of cations, especially over protons, more preferably they additionally favor the diffusion of certain anions through them over the diffusion of other anions through them.
  • cation-conducting membranes are those which selectively conduct cations, preferably selectively specific cations. In other words, they favor the diffusion of cations through them over that of anions, more preferably they additionally favor the diffusion of certain cations through them over the diffusion of other cations through them, much more preferably cations where there is are not protons, more preferably sodium cations, over protons.
  • “Favour the diffusion of certain ions X over the diffusion of other ions Y” means in particular that the diffusion coefficient (unit m 2 /s) of the ion type X at a given temperature for the membrane in question is higher by a factor of 10, preferably 100, preferably 1000 as the diffusion coefficient of the ionic species Y for the membrane in question.
  • the diffusion barrier D is a “membrane that is permeable to specific ions”, it is preferably an anion-conducting membrane because this prevents the diffusion of protons from the anode chamber K A into the middle chamber K M particularly well.
  • a membrane which is selective for the anions comprised by the salt S is used as the anion-conducting membrane.
  • Such membranes are known to those skilled in the art and can be used by them.
  • the salt S is preferably a halide, sulfate, sulfite, nitrate, bicarbonate or carbonate of X, more preferably a halide.
  • Halides are fluorides, chlorides, bromides, iodides. The most preferred halide is chloride.
  • a membrane selective for halides preferably chloride, is preferably used as the anion-conducting membrane.
  • Anion-conducting membranes are, for example, from MA Hickner, AM Herring, EB Coughlin, Journal of Polymer Science, Part B: Polymer Physics 2013, 51, 1727-1735 , from Arges CG, Ramani V, Pintauro PN, Electrochemical Society Interface 2010, 19, 31-35 , in WO 2007/048712 A2 as well as on Page 181 of the textbook by Volkmar M. Schmidt Electrochemical Process Engineering: Fundamentals, Reaction Engineering, Process Optimization, 1st edition (October 8, 2003). in.
  • they have covalently bonded functional groups selected from -NH 3 + , -NRH 2 + , -NR 3 + , more preferably selected from -NH 3 + , -NR 3 + , even more preferably -NR 3 + .
  • the diffusion barrier D is a cation-conducting membrane, it is in particular a membrane that is selective for the cations comprised by the salt S.
  • the diffusion barrier D is even more preferably an alkali cation-conducting membrane, even more preferably a potassium and/or sodium ion-conducting membrane, most preferably a sodium ion-conducting membrane.
  • Cation-conducting membranes are described, for example, in Page 181 of the textbook by Volkmar M. Schmidt Electrochemical Process Engineering: Fundamentals, Reaction Engineering, Process Optimization, 1st edition (October 8, 2003 ).
  • organic polymers which are selected in particular from polyethylene, polybenzimidazoles, polyetherketones, polystyrene, polypropylene or fluorinated membranes such as polyperfluoroethylene, preferably polystyrene, polyperfluoroethylene, are even more preferably used as the cation-conducting membrane, with these covalently bonded functional groups selected from -SO 3 - , -COO - , -PO 3 2- , -PO 2 H - , preferably -SO 3 - , (described in DE 10 2010 062 804 A1 , U.S. 4,831,146 ) carry.
  • Neosepta ® membranes are described, for example, by SA Mareev, D.Yu. Butylskii, ND Pismenskaya, C Larchet, L Dammak, VV Nikonenko, Journal of Membrane Science 2018, 563, 768-776 .
  • a cation-conducting membrane is used as the diffusion barrier D , this can be, for example, a polymer functionalized with sulfonic acid groups, in particular of the following formula P NAFION , where n and m independently of one another are an integer from 1 to 10 6 , more preferably an integer from 10 to 10 5 , more preferably is an integer from 10 2 to 10 4 .
  • the optional middle chamber K M also includes an inlet Z KM and an outlet A KM . This makes it possible to add liquid, such as solution L 3 , to the interior space I KM of the middle chamber K M , and to transfer liquid therein, such as solution L 3 , to the anode chamber K A .
  • the inlet Z KM and the outlet A KM can be attached to the electrolytic cell E by methods known to those skilled in the art, for example through bores in the outer wall W A and corresponding connections (valves) that simplify the introduction and removal of liquid.
  • the outlet A KM can also lie within the electrolytic cell, for example as a perforation in the diffusion barrier D .
  • the outlet A KM is connected to the inlet Z KA by a connection V AM in such a way that liquid can be conducted from I KM into I KA through the connection V AM ,
  • Bottom of the electrolytic cell E is, according to the invention, the side of the electrolytic cell E through which a solution (e.g. L 3 at A KM in Figure 3A) in the same direction as gravity exits the electrolytic cell E or the side of the electrolytic cell E through which a solution (e.g. L 2 at Z KK in Figures 2 A, 3 A and 3 B and L 3 at A KA in Figures 2 A, 2 B and 3 A) of the electrolytic cell E is fed against gravity.
  • “Top O E of the electrolytic cell E” is, according to the invention, the side of the electrolytic cell E through which a solution (e.g.
  • the dividing wall W is arranged in the electrolytic cell E in such a way that the solid electrolyte ceramic F , which conducts alkali cations and is enclosed by the dividing wall W , makes direct contact with the interior space I KK via the surface O KK .
  • the dividing wall W is arranged in the electrolytic cell E in such a way that when the interior space I KK is completely filled with solution L 2 , the solution L 2 contacts the surface O KK of the alkali cation-conducting solid electrolyte ceramic F enclosed by the dividing wall W ( ie wetted), so that ions (eg alkali metal ions such as sodium, lithium) from the alkali cation-conducting solid electrolyte ceramic F , which is surrounded by the partition W , can enter the solution L 2 via the surface O KK .
  • ions eg alkali metal ions such as sodium, lithium
  • the dividing wall W is arranged in the electrolytic cell E in such a way that the solid electrolyte ceramic F , which is included in the dividing wall W and which conducts alkali cations, makes direct contact with the interior space I KA via the surface O A/MK .
  • the partition wall W borders on the interior space I KA of the anode chamber K A .
  • the dividing wall W is arranged in the electrolytic cell E such that when the interior space I KA is completely filled with solution L 3 , the solution L 3 then contacts the surface O A / MK of the dividing wall W enclosed by the alkali cation-conducting solid electrolyte ceramic F (ie wetted), so that ions (eg alkali metal ions such as sodium, lithium) from the solution L 3 can enter the alkali cation-conducting solid electrolyte ceramic F , which is covered by the partition W , via the surface O A / MK .
  • ions eg alkali metal ions such as sodium, lithium
  • the partition W is arranged in the electrolytic cell E in such a way that the solid electrolyte ceramic F , which conducts alkali cations, is contained in the partition W , the interior space I KM over the surface O A/MK directly contacted.
  • the partition wall W borders on the interior space I KM of the central chamber K M .
  • the dividing wall W is arranged in the electrolytic cell E in such a way that when the interior space I KM is completely filled with solution L 3 , the solution L 3 then covers the surface O A/MK of the alkali cation-conducting solid electrolyte ceramic F surrounded by the dividing wall W contacted (ie wetted), so that ions (eg alkali metal ions such as sodium, lithium) from the solution L 3 can enter the alkali cation-conducting solid electrolyte ceramic F , which is covered by the partition W , via the surface O A / MK .
  • ions eg alkali metal ions such as sodium, lithium
  • the present invention relates to a process for preparing a solution L 1 of an alkali metal alkoxide XOR in the alcohol ROH, where X is an alkali metal cation and R is an alkyl radical having 1 to 4 carbon atoms.
  • the process is carried out in an electrolytic cell E.
  • R is preferably selected from the group consisting of n-propyl, iso -propyl, ethyl, methyl, more preferably selected from the group consisting of ethyl, methyl. Most preferably R is methyl.
  • the steps ( ⁇ 1), ( ⁇ 2), ( ⁇ 3) running simultaneously are carried out.
  • step (a1) a solution L 2 comprising the alcohol ROH, preferably comprising an alkali metal alkoxide XOR and alcohol ROH, is passed through I KK .
  • O KK comprises at least part of O F ⁇
  • the solution L 2 contacts the surface O F ⁇ directly.
  • the solution L 2 then contacts the entire surface O F ⁇ encompassed by O KK directly.
  • the solution L 2 is preferably free of water.
  • “free of water” means that the weight of the water in the solution L 2 based on the weight of the alcohol ROH in the solution L 2 (mass ratio) is ⁇ 1:10, more preferably ⁇ 1:20, even more preferably ⁇ 1:100 , more preferably ⁇ 0.5:100.
  • the mass fraction of XOR in the solution L 2 is in particular >0 to 30% by weight, preferably 5 to 20% by weight, even more preferably at 10 to 20% by weight, more preferably at 10 to 15% by weight, most preferably at 13 to 14% by weight, most preferably at 13% by weight.
  • the mass ratio of XOR to alcohol ROH in the solution L 2 is in particular in the range from 1:100 to 1:5, more preferably in the range from 1:25 to 3:20, even more preferably in the range 1:12 to 1:8, more preferably at 1:10.
  • step (a2) a neutral or alkaline, aqueous solution L 3 of a salt S comprising X as a cation is passed through I KA .
  • O A/MK comprises at least part of O F ⁇
  • the solution L 3 contacts the surface O F ⁇ directly.
  • the solution L 3 then directly contacts the entire surface O F ⁇ encompassed by O A/MK .
  • L 3 contacts the whole surface O F ⁇ directly, and in cases where O A/MK only a part of the surface O F ⁇ comprises, L 3 directly contacts the entire part of the surface O F ⁇ comprised by O A/MK .
  • the salt S is preferably a halide, sulfate, sulfite, nitrate, bicarbonate or carbonate of X, more preferably a halide.
  • Halides are fluorides, chlorides, bromides, iodides. The most preferred halide is chloride.
  • the pH of the aqueous solution L 3 is ⁇ 7.0, preferably in the range from 7 to 12, more preferably in the range from 8 to 11, even more preferably from 10 to 11, most preferably at 10.5.
  • the mass fraction of the salt S in the solution L 3 is preferably in the range > 0 to 20% by weight, preferably 1 to 20% by weight, more preferably 5 to 20% by weight, even more preferably 10 to 20% by weight %, most preferably at 20% by weight, based on the total solution L 3 .
  • step (a3) a voltage is then applied between E A and E K .
  • the charge source is known to those skilled in the art and is typically a rectifier that converts alternating current into direct current and can generate certain voltages via voltage converters.
  • the area of the solid electrolyte that contacts the anolyte in the interior I KA is in particular 0.00001 to 10 m 2 , preferably 0.0001 to 2.5 m 2 , more preferably 0.0002 to 0.15 m 2 , even more preferably 2.83 cm 2 .
  • both O A/MK and O KK comprise part of the surface O F ⁇ .
  • Step (a3) of the method is then even more preferably carried out when the interior space I KA is at least loaded with L 3 and the interior space I KK is loaded with L 2 at least to the extent that L 3 and L 2 Partition W covered surface O F ⁇ of the alkali cation-conducting solid electrolyte ceramic F contact directly.
  • the surface O F ⁇ obtained by the treatment in step (ii) takes part within both surfaces O A / MK and O KK in the electrolysis process and the advantageous properties of the alkali cation-conducting solid electrolyte ceramic F , which result in an increase in conductivity and thereby reflect an increase in current at the same voltage, have a particularly positive effect.
  • step (a3) The fact that charge transport takes place between E A and E K in step (a3) implies that I KK and I KA are loaded simultaneously with L 2 and L 3 , respectively, in such a way that they extend the electrodes E A and E K so far cover that the circuit is closed.
  • step ( ⁇ 1) and step (a2) are carried out continuously and voltage is applied in accordance with step (a3).
  • the solution L 1 is obtained at the outlet A KK , the concentration of XOR in L 1 being higher than in L 2 .
  • the concentration of XOR in L 1 is preferably 1.01 to 2.2 fold, more preferably 1.04 to 1.8 fold, even more preferably 1077 to 1.4 fold, even more preferably 1077 to 1077 fold 1.08-fold higher than in L 2 , most preferably 1,077-fold higher than in L 2 , more preferably with the mass fraction of XOR in L 1 and in L 2 being in the range 10 to 20% by weight, even more preferably 13 to 14% by weight.
  • the concentration of the cation X in the aqueous solution L 3 is preferably in the range from 3.5 to 5 mol/l, more preferably 4 mol/l.
  • the concentration of the cation X in the aqueous solution L 4 is more preferably 0.5 mol/l lower than that of the aqueous solution L 3 used in each case.
  • steps ( ⁇ 1) to ( ⁇ 3) of the process are carried out at a temperature of 20°C to 70°C, preferably 35°C to 65°C, more preferably 35°C to 60°C, even more preferably 35°C to 50 °C and a pressure of 0.5 bar to 1.5 bar, preferably 0.9 bar to 1.1 bar, more preferably 1.0 bar.
  • hydrogen is typically produced in the interior I KK of the cathode chamber K K , which hydrogen can be removed from the cell via the outlet A KK together with the solution L 1 .
  • the mixture of hydrogen and solution L 1 can then be separated by methods known to those skilled in the art.
  • the alkali metal compound used is a halide, in particular chloride, chlorine or another halogen gas can form, which can be removed from the cell via the outlet A KK together with the solution L 4 .
  • oxygen and/or carbon dioxide can also be formed, which can also be removed.
  • the mixture of chlorine, oxygen and/or CO 2 and solution L 4 can then be separated by methods known to those skilled in the art.
  • the gases chlorine, oxygen and/or CO 2 have been separated from the solution L 4 , these can be separated from one another by methods known to those skilled in the art.
  • steps ( ⁇ 1), ( ⁇ 2), ( ⁇ 3) are carried out simultaneously.
  • the electrolytic cell E comprises at least one middle chamber K M , and then the steps ( ⁇ 1), ( ⁇ 2), ( ⁇ 3) running simultaneously are carried out.
  • the solution L 2 contacts the surface O F ⁇ directly.
  • the solution L 2 then contacts the entire surface O F ⁇ encompassed by O KK directly. This means that in the cases where O KK covers the whole surface O F ⁇ , L 2 directly contacts at least a part of the surface O F ⁇ , and in the cases where O KK covers only a part of the surface O F ⁇ , L 2 directly contacts at least part of the part of the surface O F ⁇ comprised by O KK .
  • the solution L 2 is preferably free of water.
  • “free of water” means that the weight of the water in the solution L 2 based on the weight of the alcohol ROH in the solution L 2 (mass ratio) is ⁇ 1:10, more preferably ⁇ 1:20, even more preferably ⁇ 1:100 , more preferably ⁇ 0.5:100.
  • the mass fraction of XOR in the solution L 2 is in particular >0 to 30% by weight, preferably 5 to 20% by weight, even more preferably at 10 to 20% by weight, more preferably at 10 to 15% by weight, most preferably at 13 to 14% by weight, most preferably at 13% by weight.
  • the mass ratio of XOR to alcohol ROH in the solution L 2 is in particular in the range from 1:100 to 1:5, more preferably in the range from 1:25 to 3:20, even more preferably in the range 1:12 to 1:8, more preferably at 1:10.
  • step ( ⁇ 2) a neutral or alkaline aqueous solution L 3 of a salt S comprising X as a cation is passed through I KM , then over V AM , then through I KA .
  • the solution L 3 contacts the surface O F ⁇ directly.
  • the solution L 3 then directly contacts the entire surface O F ⁇ encompassed by O A/MK .
  • the salt S is preferably a halide, sulfate, sulfite, nitrate, bicarbonate or carbonate of X, more preferably a halide.
  • Halides are fluorides, chlorides, bromides, iodides. The most preferred halide is chloride.
  • the pH of the aqueous solution L 3 is ⁇ 7.0, preferably in the range from 7 to 12, more preferably in the range from 8 to 11, even more preferably from 10 to 11, most preferably at 10.5.
  • the mass fraction of the salt S in the solution L 3 is preferably in the range > 0 to 20% by weight, preferably 1 to 20% by weight, more preferably 5 to 20% by weight, even more preferably 10 to 20% by weight %, most preferably at 20% by weight, based on the total solution L 3 .
  • step ( ⁇ 3) a voltage is then applied between E A and E K .
  • the charge source is known to those skilled in the art and is typically a rectifier that converts alternating current into direct current and can generate certain voltages via voltage converters.
  • This can be determined by a person skilled in the art by default.
  • the surface of the solid electrolyte that im The anolyte contacted in the interior I KM of the middle chamber K M is in particular 0.00001 to 10 m 2 , preferably 0.0001 to 2.5 m 2 , more preferably 0.0002 to 0.15 m 2 , even more preferably 2.83 cm 2 .
  • both O A/MK and O KK comprise part of the surface O F ⁇ .
  • Step ( ⁇ 3) of the method is then even more preferably carried out when the interior space I KM is at least loaded with L 3 and the interior space I KK is loaded with L 2 at least to the extent that L 3 and L 2 Partition W covered surface O F ⁇ of the alkali cation-conducting solid electrolyte ceramic F contact directly.
  • the surface O F ⁇ obtained by the treatment in step (ii) takes part within both surfaces O A / MK and O KK in the electrolysis process and the advantageous properties of the alkali cation-conducting solid electrolyte ceramic F , which result in an increase in conductivity and thereby reflect an increase in current at the same voltage, have a particularly positive effect.
  • step ( ⁇ 3) The fact that charge transport takes place between E A and E K in step ( ⁇ 3) implies that I KK , I KM and I KA are simultaneously charged with L 2 and L 3 , respectively, in such a way that they connect the electrodes E A and E Cover K so far that the circuit is closed.
  • step ( ⁇ 1) and step ( ⁇ 2) are carried out continuously and voltage is applied in accordance with step ( ⁇ 3).
  • the solution L 1 is obtained at the outlet A KK , the concentration of XOR in L 1 being higher than in L 2 .
  • the concentration of XOR in L 1 is preferably 1.01 to 2.2 fold, more preferably 1.04 to 1.8 fold, even more preferably 1077 to 1.4 fold, even more preferably 1077 to 1077 fold 1.08-fold higher than in L 2 , most preferably 1,077-fold higher than in L 2 , more preferably with the mass fraction of XOR in L 1 and in L 2 being in the range 10 to 20% by weight, even more preferably 13 to 14% by weight.
  • the concentration of the cation X in the aqueous solution L 3 is preferably in the range from 3.5 to 5 mol/l, more preferably 4 mol/l.
  • the concentration of the cation X in the aqueous solution L 4 is more preferably 0.5 mol/l lower than that of the aqueous solution L 3 used in each case.
  • steps ( ⁇ 1) to ( ⁇ 3) of the process are carried out at a temperature of 20°C to 70°C, preferably 35°C to 65°C, more preferably 35°C to 60°C, even more preferably 35°C to 50 °C and a pressure of 0.5 bar to 1.5 bar, preferably 0.9 bar to 1.1 bar, more preferably 1.0 bar.
  • hydrogen is typically produced in the interior I KK of the cathode chamber K K , which hydrogen can be discharged from the cell together with the solution L 1 via the outlet A KK .
  • the mixture of hydrogen and solution L 1 can then be separated by methods known to those skilled in the art.
  • the alkali metal compound used is a halide, in particular chloride, chlorine or another halogen gas can form, which can be removed from the cell via the outlet A KK together with the solution L 4 .
  • oxygen and/or carbon dioxide can also be formed, which can also be removed.
  • the mixture of chlorine, oxygen and/or CO 2 and solution L 4 can then be separated by methods known to those skilled in the art.
  • the gases chlorine, oxygen and/or CO 2 have been separated from the solution L 4 , these can be separated from one another by methods known to those skilled in the art.
  • Steps ( ⁇ 1) to ( ⁇ 3) of the method according to the invention protect the acid-labile solid electrolyte from corrosion without having to sacrifice alcoholate solution from the cathode space as a buffer solution, as in the prior art. These process steps are therefore more efficient than those in WO 2008/076327 A1 described procedure in which the product solution is used for the middle chamber, which reduces the overall turnover.
  • NM Sodium methylate
  • the electrolytic cell consisted of three chambers, as in Figure 3A shown.
  • the connection between the middle and anode chamber was made by a hose that was attached to the bottom of the electrolytic cell.
  • the anode compartment and middle compartment were separated by a 33 cm 2 cation exchange membrane (Asahi Kasei, sulfonic acid groups on polymer).
  • the cathodes and middle chamber were separated by a ceramic of the NaSICON type with an area of 33 cm 2 .
  • the ceramic had a chemical composition of the formula Na 3.4 Zr 2.0 Si 2.4 P 0.6 O 12 .
  • the NaSICON ceramic used in Comparative Example 1 was cut from the same block together with two other ceramics of the same dimensions.
  • the anolyte was transferred to the anode compartment through the middle compartment.
  • the flow rate of the anolyte was 1 l/h, that of the catholyte was 1 l/h.
  • the temperature was 60°C.
  • the voltage was changed in a range from 0 to 8 V and the current was recorded. This is in Figure 4 shown. " ⁇ " indicates the measured current/voltage curve.
  • Comparative example 1 is repeated with a two-chamber cell comprising only an anode and a cathode chamber, the anode chamber being separated from the cathode chamber by a ceramic as in comparative example 1.
  • the arrangement corresponds to that in Figure 2 A shown.
  • this electrolytic cell does not contain a center chamber.
  • the mass-related specific surface of the NaSICON ceramic increased by a factor of ⁇ 3.
  • the x-axis shows the current (in mA), the y-axis shows the voltage (in volts).
  • ⁇ indicates the current/voltage curve of the non-sandblasted NaSICON ceramic.
  • ⁇ and ⁇ each indicate the current/voltage curve of the two sandblasted NaSICON ceramics.
  • Comparative example 2 is repeated using an electrolytic cell in which the solid electrolyte ceramics treated in accordance with example 1 according to the invention are used.
  • a voltage that is significantly lower than that in comparative example 2 is required for the same current intensity.
  • the conductivity of the solid electrolyte increases surprisingly due to the pretreatment (sandblasting) of the NaSICON ceramic and the exposure of the sandblasted surfaces on the interior spaces of the anode chamber or middle chamber and the cathode chamber.
  • the use of the three-chamber cell in the method of the invention also prevents corrosion of the solid electrolyte while at the same time not sacrificing an alkali metal alkoxide product for the center chamber and keeping the voltage constant.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Ceramic Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
EP21195069.6A 2021-09-06 2021-09-06 Procédé de production d'alcoolats alcalins dans une cellule d'électrolyse Withdrawn EP4144890A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
EP21195069.6A EP4144890A1 (fr) 2021-09-06 2021-09-06 Procédé de production d'alcoolats alcalins dans une cellule d'électrolyse
EP22765897.8A EP4399349A1 (fr) 2021-09-06 2022-08-19 Procédé de production d'alcoolates de métaux alcalins dans une cellule d'électrolyse
PCT/EP2022/073158 WO2023030920A1 (fr) 2021-09-06 2022-08-19 Procédé de production d'alcoolates de métaux alcalins dans une cellule d'électrolyse
US18/688,762 US12503783B2 (en) 2021-09-06 2022-08-19 Method for producing alkali metal alcoholates in an electrolysis cell

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP21195069.6A EP4144890A1 (fr) 2021-09-06 2021-09-06 Procédé de production d'alcoolats alcalins dans une cellule d'électrolyse

Publications (1)

Publication Number Publication Date
EP4144890A1 true EP4144890A1 (fr) 2023-03-08

Family

ID=77640592

Family Applications (2)

Application Number Title Priority Date Filing Date
EP21195069.6A Withdrawn EP4144890A1 (fr) 2021-09-06 2021-09-06 Procédé de production d'alcoolats alcalins dans une cellule d'électrolyse
EP22765897.8A Pending EP4399349A1 (fr) 2021-09-06 2022-08-19 Procédé de production d'alcoolates de métaux alcalins dans une cellule d'électrolyse

Family Applications After (1)

Application Number Title Priority Date Filing Date
EP22765897.8A Pending EP4399349A1 (fr) 2021-09-06 2022-08-19 Procédé de production d'alcoolates de métaux alcalins dans une cellule d'électrolyse

Country Status (3)

Country Link
US (1) US12503783B2 (fr)
EP (2) EP4144890A1 (fr)
WO (1) WO2023030920A1 (fr)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP4144888A1 (fr) 2021-09-06 2023-03-08 Evonik Functional Solutions GmbH Procédé de production d'alcoolats alcalins dans une cellule d'électrolyse

Citations (22)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DD258143A3 (de) 1986-03-03 1988-07-13 Koethen Ing Hochschule Elektrolysezelle fuer stofftransportgehemmte oder durch konzentrationsabnahmen kinetisch verlangsamte elektrodenreaktionen
US4831146A (en) 1988-03-21 1989-05-16 Air Products And Chemicals, Inc. Process for preparing triacetone amine and other oxopiperidines
DE4233191A1 (de) 1992-01-16 1993-07-22 Huels Chemische Werke Ag Verfahren zur herstellung von alkoholaten
US5389211A (en) 1993-11-08 1995-02-14 Sachem, Inc. Method for producing high purity hydroxides and alkoxides
US6221225B1 (en) 1997-01-23 2001-04-24 Archer Daniels Midland Company Apparatus and process for electrodialysis of salts
WO2005059205A2 (fr) 2003-12-11 2005-06-30 American Pacific Corporation Procede electrolytique de fabrication d'alcoolates d'alcali au moyen de membranes solides ceramiques conduisant les ions
DE10360758A1 (de) 2003-12-23 2005-07-28 Degussa Ag Elektrochemische Herstellung von Alkalialkoholaten mit Hilfe einer keramischen Festelektrolytmembran
US20060226022A1 (en) 2003-12-11 2006-10-12 Ceramatec, Inc. Electrolytic method to make alkali alcoholates using ceramic ion conducting solid membranes
WO2007048712A2 (fr) 2005-10-24 2007-05-03 Basf Se Membranes structurees en surface, membranes revetues de catalyseur et unites membrane-electrode composees de ces membranes
US20070138020A1 (en) * 2005-12-20 2007-06-21 Shekar Balagopal Electrolytic process to produce sodium hypochlorite using sodium ion conductive ceramic membranes
WO2007082092A2 (fr) 2006-01-11 2007-07-19 Ceramatec, Inc. Synthese de biodiesel au moyen de membranes ceramiques conductrices d'ions de metal alcalin
WO2008076327A1 (fr) 2006-12-14 2008-06-26 Ceramatec, Inc. Procédé électrolytique de production d'alcoolates alcalins dans lequel sont utilisés et un séparateur et un électrolyte alcalins conducteurs d'ions
US20080173540A1 (en) * 2003-12-11 2008-07-24 Joshi Ashok V Electrolytic Cell for Producing Alkali Alcoholates
WO2009059315A1 (fr) 2007-11-02 2009-05-07 Ceramatec, Inc Processus électrolytique pour séparer des ions de métaux alcalins de sels alcalins de glycérine
US20100044242A1 (en) 2008-08-25 2010-02-25 Sai Bhavaraju Methods For Producing Sodium Hypochlorite With a Three-Compartment Apparatus Containing an Acidic Anolyte
DE102010062804A1 (de) 2010-01-12 2011-07-14 Evonik Degussa GmbH, 45128 Verfahren zur Herstellung von 1,1 Diarylalkanen und Derivativen davon
US20120085657A1 (en) * 2010-10-07 2012-04-12 Sai Bhavaraju Chemical systems and methods for operating an electrochemical cell with an acidic anolyte
WO2014008410A1 (fr) 2012-07-03 2014-01-09 Ceramatec, Inc. Appareil et procédé de production de métal dans une cellule électrolytique de nasicon
US20160204459A1 (en) 2015-01-13 2016-07-14 Korea Institute Of Science And Technology Porous nafion membrane and method for preparing the same
DE102015013155A1 (de) 2015-10-09 2017-04-13 Forschungszentrum Jülich GmbH Elektrolytmaterial mit NASICON-Struktur für Feststoff-Natriumionenbatterien sowie Verfahren zu deren Herstellung
US20190292668A1 (en) * 2018-03-22 2019-09-26 Sekisui Chemical Co., Ltd. Carbon dioxide reduction apparatus and method of producing organic compound
CN112736364A (zh) * 2020-12-28 2021-04-30 惠州亿纬创能电池有限公司 一种复合隔膜及其制备方法和应用

Family Cites Families (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE258143C (fr)
CN102544579A (zh) 2010-12-07 2012-07-04 中国电子科技集团公司第十八研究所 一种水体系锂电池固体电解质片的刻蚀方法
EP3885470B1 (fr) 2020-03-24 2023-06-28 Evonik Operations GmbH Procédé de fabrication d'alcooliques métalliques alcalins dans une cellule d'électrolyse à trois chambres
EP3885471B1 (fr) 2020-03-24 2023-07-19 Evonik Operations GmbH Procédé amélioré de fabrication d'alcools de sodium
ES2958263T3 (es) 2021-02-11 2024-02-06 Evonik Operations Gmbh Procedimiento de producción de alcoholatos de metales alcalinos en una celda electrolítica de tres cámaras
PL4112778T3 (pl) 2021-06-29 2024-05-13 Evonik Operations Gmbh Trójkomorowe ogniwo elektrolityczne do wytwarzania alkoholanów metali alkalicznych
EP4112780B1 (fr) 2021-06-29 2023-08-02 Evonik Operations GmbH Cellule d'électrolyse à trois chambre destinée à la production d'alcoolates alcalimétaux
HUE064033T2 (hu) 2021-06-29 2024-02-28 Evonik Operations Gmbh Háromkamrás elektrolízis cella alkálifémalkoholátok elõállítására
EP4124677A1 (fr) 2021-07-29 2023-02-01 Evonik Functional Solutions GmbH Paroi de séparation résistante à la rupture comprenant des céramiques à électrolyte solide pour cellules d'électrolyse
EP4124675B1 (fr) 2021-07-29 2024-07-10 Evonik Operations GmbH Paroi de séparation résistante à la rupture comprenant des céramiques à électrolyte solide pour cellules d'électrolyse
EP4134472A1 (fr) 2021-08-13 2023-02-15 Evonik Functional Solutions GmbH Procédé de production d'alcoolats alcalins dans une cellule d'électrolyse
EP4144889A1 (fr) 2021-09-06 2023-03-08 Evonik Functional Solutions GmbH Procédé de production d'alcoolats alcalins dans une cellule d'électrolyse
EP4144888A1 (fr) 2021-09-06 2023-03-08 Evonik Functional Solutions GmbH Procédé de production d'alcoolats alcalins dans une cellule d'électrolyse

Patent Citations (24)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DD258143A3 (de) 1986-03-03 1988-07-13 Koethen Ing Hochschule Elektrolysezelle fuer stofftransportgehemmte oder durch konzentrationsabnahmen kinetisch verlangsamte elektrodenreaktionen
US4831146A (en) 1988-03-21 1989-05-16 Air Products And Chemicals, Inc. Process for preparing triacetone amine and other oxopiperidines
DE4233191A1 (de) 1992-01-16 1993-07-22 Huels Chemische Werke Ag Verfahren zur herstellung von alkoholaten
US5389211A (en) 1993-11-08 1995-02-14 Sachem, Inc. Method for producing high purity hydroxides and alkoxides
US6221225B1 (en) 1997-01-23 2001-04-24 Archer Daniels Midland Company Apparatus and process for electrodialysis of salts
US20080173540A1 (en) * 2003-12-11 2008-07-24 Joshi Ashok V Electrolytic Cell for Producing Alkali Alcoholates
WO2005059205A2 (fr) 2003-12-11 2005-06-30 American Pacific Corporation Procede electrolytique de fabrication d'alcoolates d'alcali au moyen de membranes solides ceramiques conduisant les ions
US20060226022A1 (en) 2003-12-11 2006-10-12 Ceramatec, Inc. Electrolytic method to make alkali alcoholates using ceramic ion conducting solid membranes
DE10360758A1 (de) 2003-12-23 2005-07-28 Degussa Ag Elektrochemische Herstellung von Alkalialkoholaten mit Hilfe einer keramischen Festelektrolytmembran
WO2007048712A2 (fr) 2005-10-24 2007-05-03 Basf Se Membranes structurees en surface, membranes revetues de catalyseur et unites membrane-electrode composees de ces membranes
US20070138020A1 (en) * 2005-12-20 2007-06-21 Shekar Balagopal Electrolytic process to produce sodium hypochlorite using sodium ion conductive ceramic membranes
WO2007082092A2 (fr) 2006-01-11 2007-07-19 Ceramatec, Inc. Synthese de biodiesel au moyen de membranes ceramiques conductrices d'ions de metal alcalin
WO2008076327A1 (fr) 2006-12-14 2008-06-26 Ceramatec, Inc. Procédé électrolytique de production d'alcoolates alcalins dans lequel sont utilisés et un séparateur et un électrolyte alcalins conducteurs d'ions
WO2009073062A2 (fr) 2007-10-01 2009-06-11 Ceramatec, Inc. Cellule électrolytique servant à produire des alcoolates alcalins
WO2009059315A1 (fr) 2007-11-02 2009-05-07 Ceramatec, Inc Processus électrolytique pour séparer des ions de métaux alcalins de sels alcalins de glycérine
US20100044242A1 (en) 2008-08-25 2010-02-25 Sai Bhavaraju Methods For Producing Sodium Hypochlorite With a Three-Compartment Apparatus Containing an Acidic Anolyte
DE102010062804A1 (de) 2010-01-12 2011-07-14 Evonik Degussa GmbH, 45128 Verfahren zur Herstellung von 1,1 Diarylalkanen und Derivativen davon
US20120085657A1 (en) * 2010-10-07 2012-04-12 Sai Bhavaraju Chemical systems and methods for operating an electrochemical cell with an acidic anolyte
WO2012048032A2 (fr) 2010-10-07 2012-04-12 Ceramatec, Inc. Systèmes et procédés chimiques pour faire fonctionner une cellule électrochimique avec un anolyte acide
WO2014008410A1 (fr) 2012-07-03 2014-01-09 Ceramatec, Inc. Appareil et procédé de production de métal dans une cellule électrolytique de nasicon
US20160204459A1 (en) 2015-01-13 2016-07-14 Korea Institute Of Science And Technology Porous nafion membrane and method for preparing the same
DE102015013155A1 (de) 2015-10-09 2017-04-13 Forschungszentrum Jülich GmbH Elektrolytmaterial mit NASICON-Struktur für Feststoff-Natriumionenbatterien sowie Verfahren zu deren Herstellung
US20190292668A1 (en) * 2018-03-22 2019-09-26 Sekisui Chemical Co., Ltd. Carbon dioxide reduction apparatus and method of producing organic compound
CN112736364A (zh) * 2020-12-28 2021-04-30 惠州亿纬创能电池有限公司 一种复合隔膜及其制备方法和应用

Non-Patent Citations (5)

* Cited by examiner, † Cited by third party
Title
KREUER K D ET AL: "NASICON solid electrolytes part III: Sodium conductivity enhancement along domain and grain boundaries", MATERIALS RESEARCH BULLETIN, ELSEVIER, KIDLINGTON, GB, vol. 21, no. 2, 1 February 1986 (1986-02-01), pages 149 - 159, XP024184418, ISSN: 0025-5408, [retrieved on 19860201], DOI: 10.1016/0025-5408(86)90201-1 *
M.A. HICKNERA.M. HERRINGE.B. COUGHLIN, JOURNAL OF POLYMER SCIENCE, PART B: POLYMER PHYSICS, vol. 51, 2013, pages 1727 - 1735
N. ANANTHARAMULUK. KOTESWARA RAOG. RAMBABUB. VIJAYA KUMARVELCHURI RADHAM. VITHAL, J MATER SEI, vol. 46, 2011, pages 2821 - 2837
S.A. MAREEVD.YU. BUTYLSKIIN.D. PISMENSKAYAC. LARCHETL. DAMMAKV.V. NIKONENKO, JOURNAL OF MEMBRANE SCIENCE, vol. 563, 2018, pages 768 - 776
V. RAMANIP.N. PINTAURO, ELECTROCHEMICAL SOCIETY INTERFACE, vol. 19, 2010, pages 31 - 35

Also Published As

Publication number Publication date
US20240384426A1 (en) 2024-11-21
EP4399349A1 (fr) 2024-07-17
US12503783B2 (en) 2025-12-23
WO2023030920A1 (fr) 2023-03-09

Similar Documents

Publication Publication Date Title
EP3885470B1 (fr) Procédé de fabrication d'alcooliques métalliques alcalins dans une cellule d'électrolyse à trois chambres
EP3885471B1 (fr) Procédé amélioré de fabrication d'alcools de sodium
EP4043616B1 (fr) Procédé de production d'alcooliques métalliques alcalins dans une cellule d'électrolyse à trois chambres
EP4112780B1 (fr) Cellule d'électrolyse à trois chambre destinée à la production d'alcoolates alcalimétaux
DE2844499C2 (de) Verfahren zum Herstellen eines Halogens
EP4112778B1 (fr) Cellule d'électrolyse à trois chambre destinée à la production d'alcoolates alcalimétaux
EP4112779B1 (fr) Cellule d'électrolyse à trois chambre destinée à la production d'alcoolates alcalimétaux
DE2926560A1 (de) Elektrolysezelle, membran-elektroden- einheit und verfahren zur herstellung von halogen und alkalimetallhydroxid
DE3020260C2 (fr)
DE10030093C1 (de) Verfahren und Vorrichtung zur Herstellung von Metallhydroxiden oder basischen Metallcarbonaten
WO2023016897A1 (fr) Procédé de production d'alcoolates de métal alcalin dans une cellule d'électrolyse
DE2260771B2 (de) Verfahren zur herstellung von alkalihydroxid und chlor oder wasserstoff und chlor durch elektrolyse
EP4124675B1 (fr) Paroi de séparation résistante à la rupture comprenant des céramiques à électrolyte solide pour cellules d'électrolyse
EP4377498A1 (fr) Paroi de séparation résistante à la rupture entourant des céramiques à électrolyte solide pour cellules d'électrolyse
EP4399347A1 (fr) Procédé de production d'alcoolates de métaux alcalins dans une cellule d'électrolyse
EP4144890A1 (fr) Procédé de production d'alcoolats alcalins dans une cellule d'électrolyse
DE10119285B4 (de) Verfahren zum Betreiben einer Chlor-Alkali-Elektrolysezelle
EP4144888A1 (fr) Procédé de production d'alcoolats alcalins dans une cellule d'électrolyse
DE19926887A1 (de) Elektrolyseverfahren
EP2037005B1 (fr) Procédé de fabrication d'électrodes de graphite pour des processus électrolytiques
DD209856A5 (de) Poroeses plattenfoermiges diaphragma
DE2409193C3 (de) Elektrolysezelle und ihre Verwendung zur Chloralkali-Elektrolyse
DE2745542A1 (de) Verfahren zur elektrolyse von salzloesungen durch quecksilberkathoden

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION HAS BEEN PUBLISHED

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: EVONIK OPERATIONS GMBH

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN

18D Application deemed to be withdrawn

Effective date: 20230909